Gas barrier film, substrate film, and organic electroluminescence device

ABSTRACT

A gas barrier film comprising a gas barrier laminate on a substrate film, in which the gas barrier laminate comprises at least one three-layer unit consisting of a silicon nitride layer, a silicon carbide compound layer, and a silicon nitride layer disposed in this order being adjacent with each other.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a gas barrier film and, morespecifically, it relates to a laminate type gas barrier film suitable tosubstrates for various kinds of devices and coating films for thedevices. Further, the invention also relates to an organicelectroluminescence device excellent in durability and flexibilityobtained by using the gas barrier film (referred to hereinafter as anorganic EL device).

2. Description of the Related Art

Gas barrier films in which thin films of metal oxide such as aluminumoxide, magnesium oxide, and silicon oxides are formed on the surfaces ofplastic substrates or films have been generally used so far forpackaging of articles requiring shielding of steams or various gasessuch as oxygen, or packaging application for preventing denaturation offoodstuffs, industrial products, and medicines. Further, the gas barrierfilms have also been started for use in substrates of liquid crystaldisplay devices, solar cells or EL devices in addition to the packaginguse. Particularly, in transparent substrates which have been appliedprogressively to liquid crystal display devices, EL devices, etc., highlevel of demands such as long time reliability, high degree of freedomin view of shape, and capability of display on a curved surface havebeen required in addition to the demand for reduction in the weight andincrease in the size.

Recently, in the field of the liquid crystal display devices, the ELdevices, etc., film substrates such as made of transparent plastics havebeen started for use instead of glass substrates, which are heavy,tended to be cracked and difficult in increasing the area. Further,since the plastic substrates such as made of transparent plastics notonly can cope with the requirements described above but also can beapplied to the roll-to-roll system, they are advantageous over glassmaterials in view of the productivity and the reduction of cost.However, film substrates such as of transparent plastics involve aproblem of poor gas barrier property in comparison with glass. Sincesteam or air permeates in a case of a substrate of poor gas barrierproperty, when it is used for example to a liquid crystal displaydevice, liquid crystals in a liquid crystal cell are deteriorated anddeteriorated portions result in display defects to deteriorate thedisplay quality.

For solving such problems, it has been known to form a thin film of ametal oxide on the film substrate described above, and use the gasbarrier film as a transparent substrate. As gas barrier films used forpackaging materials and liquid crystal display devices, those formed byvapor depositing silicon oxide on a plastic film (for example, in JP-BNo. 53-12953 (p1 to p3) and those formed by vapor depositing aluminumoxide (for example, in JP-A No. 58-217344 (p1 to p4)) are known and theyhave a steam barrier property of about 1 g/m²/day. However, the steambarrier property as low as about 0.1 g/m²/day has been demanded recentlyfor the film substrate along with increase in the size of liquid crystaldisplays or development for highly fine displays.

Further, most recently, development has been progressed, for example, inorganic EL displays or highly fine color liquid crystal displaysrequiring further higher barrier property and it has been demanded for asubstrate having a performance of higher barrier property, particularly,a steam barrier property of less than 0.1 g/m²/day while maintainingtransparency usable therein.

For coping with such a demand, film formation by way of a sputteringmethod or a CVD method of forming a thin film using plasmas generated byglow discharge under low pressure conditions has been studied as meanscapable of expecting highly barrier performance. Further, it has beenattempted to obtain desired performance by lamination structure (forexample, in JP-A No. 2003-206361 (p2-p3)).

However, in a case of using the film substrate, since restriction isimposed on the substrate temperature during film formation, a barrierlayer of a sufficiently dense structure can not be formed, and a filmhaving a barrier property enough to satisfy the requirement has not yetbeen manufactured.

Further, with an aim of improving adhesion between the substrate and thebarrier layer, a technique of providing a silicon carbide compound layerbetween both of them has been proposed (refer, for example, to JP-A No.2003-340971 (P3 to P9)).

However, this is merely applied to a single barrier layer and has notyet developed a barrier function required in organic EL devices, etc.

On the other hand, it has been proposed a technique of preparing abarrier film having an alternate laminate structure of organiclayer/inorganic layer by a vapor deposition method (for example, referto U.S. Pat. No. 6,413,645B1 (p4, [2-54] to p8, [8-22])) and “Thin Solidfilms” written by Affinito, et al., (1996), p. 290 to p291 (p63 top67)), and a film having a barrier property necessary for the filmsubstrate for organic EL device is obtained.

However, in a case of continuously forming the films for the organiclayer and the inorganic layer, it gives rise to a problem such ascontamination between both of the process, and it is necessary to form amulti-layered structure of at least six or more layers in order toprovide a barrier film of high reliability for use in organic ELdevices. Since it has been difficult to make the performance and thehigh throughput compatible, it has been demanded for developing a newfilm forming system suitable to continuous film forming process.

SUMMARY OF THE INVENTION

For overcoming the foregoing problems, an object of the presentinvention is to provide a film of high gas barrier property having highproductivity suitable to continuous film formation. Another object ofthe present invention is to provide an organic EL device having highdurability, and excellent in flexibility free of deterioration of imagequality even during long time use.

The present inventor, as a result of an earnest study, has found thatthe subject can be solved with the following constitutions.

-   (1) A gas barrier film comprising a gas barrier laminate on a    substrate film, in which the gas barrier laminate comprises at least    one three-layer unit consisting of a silicon nitride layer, a    silicon carbide compound layer, and a silicon nitride layer disposed    in this order being adjacent with each other.-   (2) A gas barrier film described in (1), having a permeability at    40° C. and 90% relative humidity is 0.01 g/m². day or less.-   (3) A gas barrier film described in (1) or (2), wherein the    substrate film is formed of a polymeric material having a glass    transition temperature of 120° C. or higher.-   (4) A gas barrier film described in any one of (1) to (3), wherein    at least one of the silicon nitride layers in the gas barrier film    is formed by using inductively coupled plasma CVD.-   (5) A gas barrier film described in any one of (1) to (4), wherein    the silicon carbide compound layer has a ratio between silicon atom    and carbon atom of 1:1 to 10:1.-   (6) A gas barrier film described in (5), wherein the silicon carbide    compound layer contains oxygen atom and the constituent ratio of    carbon atom and oxygen atom is from 1:1 to 1:5.-   (7) A gas barrier film described in any one of (1) to (6), wherein    the substrate film is a film comprising a polymer having a structure    represented by the following formula (1) or a film comprising a    polymer having a structure represented by the following formula (2):

wherein a ring α represents a mononuclear or polynuclear ring and tworings may be identical or different with each other and are bonded byspiro bonding,

wherein a ring β and a ring γ each represents a mononuclear orpolynuclear ring, two rings γ may be identical or different with eachother and connected to one quaternary carbon on the ring β.

-   (8) A gas barrier film described in any one of (1) to (7), wherein a    transparent conductive layer is disposed on the gas barrier    laminate.-   (9) A gas barrier film described in any one of (1) to (8),    manufactured by a method of supplying the substrate film in a    roll-to-roll system and forming the gas barrier laminate    continuously.-   (10) A substrate film for use in an image display device using a gas    barrier film described in any one of (1) to (9).-   (11) An organic electroluminescence device using a substrate film    for use in an image display device described in (10).-   (12) An organic electroluminescence device manufactured by forming    the organic electroluminescence device described in-   (11), then disposing at lest one three-layer unit consisting of a    silicon nitride layer, a silicon carbide compound layer, and a    silicon nitride layer disposed in this order being adjacent with    each other in vacuum without exposing to atmospheric air and then    sealing them.

According to the invention, a film having a high gas barrier propertycan be provided by a manufacturing method having high productivitysuitable to continuous film formation can be provided. Further, theinvention can provide an organic EL device free of degradation of imagequality even during long time use, having high durability and excellentin flexibility.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is an explanatory view showing an inductively coupled plasma CVDapparatus used for manufacturing of Specimens Nos. 1 to ; and

FIG. 2 is an explanatory view showing a sputtering apparatus used formanufacturing Specimens Nos. 20 and 21.

BEST MODE FOR CARRYING OUT THE INVENTION

The gas barrier film according to the present invention is to bedescribed specifically below. Explanation for the constituent factors tobe described later are sometimes based on typical embodiments of theinvention but the invention is not restricted to such embodiments. Inthe specification, ranges for numeral values represented by “ - - -to - - - ” means ranges including numeral values described before andafter “to” as the lower limit value and the upper limit value.

Gas Barrier Film

In the gas barrier film according to the invention, a gas barrierlaminate formed on the substrate film comprises at least one unitcomprising three layers of a silicon nitride layer, a silicon carbidecompound layer, and a silicon nitride layer disposed in this order beingadjacent with each other. The silicon nitride layer referred to hereinmeans a layer comprising silicon nitride as a main ingredient and thesilicon carbide compound layer means a layer comprising silicon carbidecompound as a main ingredient. The main ingredient referred to hereinmeans such an ingredient that the total of the elements of silicon andnitrogen for the silicon nitride layer, or the total of the elements ofsilicon, carbon, and oxygen for the silicon carbide compound layer is,preferably, 90 mass % or more, more preferably, 95 mass % or more and,further preferably, 98 mass % or more based on the total elementsconstituting the entire layer. The gas barrier film of the invention canbe optionally provided further with an organic layer or a functionallayer such as a protective layer, a hygroscopic layer, an antistaticlayer, etc.

Gas Barrier Layer

The silicon nitride contained in the silicon nitride layer means acomposition in which the main constituent element comprises silicon andnitrogen. It is preferred for the starting material for forming the filmthat each of other constituent elements than described above such assmall amount of oxygen, hydrogen, carbon, etc. intruded from thesubstrate, atmospheric air, etc. is less than 5%. The constituent ratiofor silicon atom and nitrogen atom constituting the silicon nitride inthe invention represented by the compositional formula: Si₃N_(x) ispreferably: x=3.15 to 4.00. At x=3.15 or more, the film is less coloredand the gas barrier property can be ensured. Preferably, x=3.50 to 4.00and, most preferably, x=4.00 which is a stoichiometrical compositionalratio.

Two silicon nitride layers sandwiching the silicon carbide compoundlayer in the invention may be each of an identical composition orcompositions different from each other so long as the main ingredient issilicon nitride.

Silicon carbide compound of the invention means a composition in whichthe main constituent elements comprise silicon and carbide. Preferably,it is a composition at least containing 10% or more of oxygen inaddition to silicon and carbon. It is preferred that each of theconstituent elements other than silicon carbon, and oxygen is less than10%. Other constituent elements than silicon, carbon, and oxygen mean asmall amount of hydrogen, nitrogen, etc. intaken from starting materialsfor film formation, substrate, atmosphere, etc.

Ratio for silicon atom, carbon atom and oxygen atom constituting thesilicon carbide compound of the invention represented by thecompositional formula: Si_(y)O_(z)C_(w), is preferably: 3.15<r≦4.0 andy/w=1 to 10, assuming r=(2z+4w)/y. In a case where r is 3.15 or less,the film is colored remarkably and the gas barrier property is alsodeteriorated. In case where y/w is 10 or less, the strength of thebarrier layer is high. In a case where y/w is 1 or more, the inter-layeradhesion with respect to the adjacent silicon nitride layer is favorableand, further, the film tends to be peeled. y/w is, more preferably, from1 to 5 and, further preferably, from 2 to 4. Further, z/y is,preferably, from 0 to 2, more preferably, from 0.2 to 1.5 and, mostpreferably, from 0.5 to 1.0, and z/w is, preferably, from 1 to 5, morepreferably, from 1 to 3 and, most preferably, from 1 to 2.

The elemental ratio of the laminate specimen of the invention can bemeasured by a known standard method according to X-ray photoelectronspectroscopy (XPS) while etching.

The refractive index of the two silicon nitride layers gives nosignificant effects on the gas barrier performance and it does notrestrict the invention and it is preferred that the refractive index foreach of them is within a range from 1.7 to 2.2. A gas barrierperformance can be ensured at a refractive index of 1.7 or higher andthe application range of the gas barrier film is extended at arefractive index of 2.2 or lower since absorption in a visible range isweak.

For the method of forming the gas barrier layer of the invention, anymethod can be used so long as an aimed thin film can be formed. Forexample, a sputtering method, a vapor deposition method, an ion platingmethod, or a plasma CVD method is suitable and, specifically, formationmethods described in each of JP No. 3400324, JP-A Nos. 2002-322561, and2002-361774 can be adopted.

The steam permeability of the gas barrier film of the invention at 40°C. and 90% relative humidity is, preferably, 0.1 g/m².day or less, morepreferably, 0.05 g/m².day or less and, particularly preferably, 0.01g/m².day or less while this depends on the application use.

For manufacturing a gas barrier film having a high barrier property witha steam permeability of 0.01 g/m².day or less at 40° C. and 90% relativehumidity, it is preferred to adopt any of the forming methods of aninductively coupled plasma CVD, or PDV or CVD using plasmas withapplication of microwaves and magnetic fields set to the electroncyclotron resonance condition is preferred, and the use of the formationmethod according to the inductively coupled plasma CVD is mostpreferred. The inductively coupled plasma CVD or CVD using plasmas withapplication of microwaves and magnetic fields set to the electroncyclotron resonance condition (ECR-CVD) can be practiced according tothe method as described, for example in, CVD Handbook, p.284 (1991) byChemical Engineering Society. Further, PVD using plasmas withapplication of microwaves and magnetic fields set to the electroncyclotron resonance condition (ECR-PVD) can be practiced for example bythe method described by Ono, et al. in Jpn, J. Appl. Phys. 23, No. 8,L534 (1984).

As the starting material for forming the silicon nitride in a case ofusing CVD, a gas source such as a silicon halide typically representedby silane or dichlorosilane or a liquid source such as hexamethyldisilazane as a silicon supply source can be used. As a nitrogen supplysource, a gas source such as nitrogen or ammonia or a liquid source suchas hexamethyl disilazane can be used.

For providing high barrier performance, combination of a silane gas ofhigh reactivity and nitrogen is most preferred.

Generally, when a substrate film is put in a vacuum vessel, water,residual solvents, surface adsorption ingredients, or trace amounts oflow molecular residual ingredients are released from the film surface.For forming a gas barrier layer of a dense structure, it is preferred todecrease the releasing ingredients. Specifically, a pre-treatment ofintroducing the film into the vacuum vessel before film formation orpreheating the film to remove the releasing ingredients is effective. Inthis regard, use of a highly heat resistant substrate is effective.

Further, in a case of using a highly heat resistant substrate, thesubstrate can be heated upon formation of the gas barrier layer ortransparent conductive layer and since this promotes re-arrangement ofthe molecules or atoms during film formation, a gas barrier film and atransparent conductive film having gas barrier property at higherquality can be obtained.

As the starting material for forming the silicon carbide compound in acase of using CVD, one or more of known silicon carbide compounds suchas hexamethyl disiloxane (HMDSO), 1,1,3,3-tetramethyl disiloxane(TDMSO), tetramethyl silane (TMS), vinyl trimethoxy silane, vinyltrimethyl silane, dimethyl dimethoxy silane, tetramethoxy silane (TMOS),methyl trimethoxy silane, dimethyl diethoxy silane, trimethyl methoxysilane, tetraethoxy silane (TEOS), diethyl diethoxy silane,methyldimethoxy silane, methyl diethoxy siloxane, methyl diethoxysiloxane, normal methyl trimethoxy silane, and hexamethyl disilazane(HMDSN) containing nitrogen can be used in combination. Among them,silicon carbide compounds having two or more alkyl groups are preferred,with hexamethyl disiloxane (HMDSO) being more preferred.

With an aim of promoting the reaction of the silicon carbide compound,oxygen as an oxygen source, nitrogen and ammonia as a nitrogen source,dinitrogen monoxide as the oxygen source and the nitrogen source, andcarbon compounds such as CH₄, C₂H₂, C₂H₄, C₂H₆, C₂F₂, C₂F₄, C₂F₆, andC₃H₈ may also be used together as the carbon source. As the carbonsource, C₂H₂ or C₂H₄ is used preferably.

While the thickness of the gas barrier layer is not particularlylimited, the substrate may possibly cause warping, deformation, etc.along with occurrence of cracks or increase of internal stress due tobending stress in a case where it is excessively thick, or the filmdistributes in an island-shape in a case where it is excessively thinfor each of the layers, so that the steam barrier property tends to beworsened in each of the cases. This trend develops particularlyremarkably in the silicon carbide compound layer.

Accordingly, the thickness of the silicon nitride layer is within arange, preferably, from 20 to 500 nm, more preferably, 50 nm to 200 nm,most preferably, 80 to 150 nm. Each of two or more silicon nitridelayers may have an identical film thickness or have differentcompositions, which is not particularly limited so long as this iswithin the range described above.

It is preferred that the thickness of the silicon carbide compound layeris larger than that of the adjacent two silicon nitride layers and it isdesirably within a range from 100 to 1,000 nm. At a thickness of 100 nmor more, sufficient barrier property can be expected, and at a thicknessof 1,000 nm or less, the silicon nitride layer, adjacent on the externalside can be made less fractured.

With an aim of enhancing the reliability, a silicon carbide compoundlayer, silicon nitride layer, etc. may further be laminated to thecontinuous silicon nitride layer . silicon carbide compound layer .silicon nitride layer of the invention. However, also in this case, thetotal thickness of the layer thickness does not preferably exceed 1500nm.

It is a well-known technique in the relevant field to control to desiredoptical characteristics by determining the refractive index of each ofthe layers and controlling the effect caused by the optical interferenceof the inter-layer reflection light in the laminate film by controllingthe thickness for each of the layers. It will be apparent that thecharacteristics can be controlled without degrading the barrierperformance.

A desired functional layer can be disposed optionally between the gasbarrier laminate and the substrate film, and/or to the outside of thegas barrier laminate and at the back surface of the substrate film. Anexample of the functional layer disposed between the gas barrierlaminate and the substrate film includes a smoothing layer, an adhesionimproving layer, a light shielding layer including a black matrix, ananti-reflection layer, etc. It may also be a thin inorganic film layerformed by a CVD or PVD method, or it may be a layer formed by forming aUV-ray or electron beam curable monomer, oligomer or resin by coating orvapor deposition and then curing the same by UV-rays or electron beams.

In the same manner, a known functional layer may also be disposed to theoutside and/or inside of the gas barrier laminate as viewed on the sideof the substrate. As the example of the functional layer, knownfunctional layers such as a protective layer for providing scratchresistance, an anti-hauling layer, an anti-static layer, ananti-reflective layer, an anti-dazzling layer, an anti-adhesion layer, ahygroscopic layer, a solvent resistance layer, a color filter can beused.

Particularly, it is effective to dispose a transparent conductive layersuch as of ITO or IZO to the outermost layer of the gas barrier filmaccording to the invention for utilizing as the substrate for theelectron device. For the transparent conductive layer, known vacuum filmforming method such as a sputtering method or ion plating method orcoating method utilizing sol-gel method can be utilized and a vacuumfilm forming method of continuously forming the film without returningthe pressure to the atmospheric pressure upon formation of the gasbarrier laminate is advantageous with the viewpoint of the manufacturingcost, and ensured of reliability and inter-layer adhesion.

Further, since the gas barrier film is excellent in the bendingresistance, it can be formed continuously into a film by a roll-to-rollmethod. Further, since the composition in each of the layers is similar,it is not necessary to strictly partition the film forming area betweeneach of the layers and it less suffers from degradation of theperformance by contamination, so that it has a merit capable of easilyobtaining the advantage particularly of the roll-to-roll method becauseof the production cost, reliability and simplification of maintenance.

Further, a different or identical substrate film may be used beingsuperposed on the gas barrier substrate of the invention by a method byway of a heat sealing material with an aim of protection.

Substrate Film

The substrate film to be used for the gas barrier film of the inventionis not particularly restricted so long as it is a film capable ofmaintaining each of the layers, and can be optionally selected inaccordance with the use. The substrate film specifically includes, forexample, thermoplastic resins such as polyester resin, methacrylicresin, methacrylic acid-maleic acid copolymer, polystyrene, transparentfluoro-resin, polyimide resin, fluorinated polyimide resin, polyamideresin, polyamideimide resin, polyether imide resin, cellulose acylateresin, polyurethane resin, polyether ether ketone resin, polycarbonateresin, cycloaliphatic polyolefin resin, polyarylate resin, polyethersulfone resin, polysulfone resin, cycloolefine copolymer, fluolenering-modified carbonate resin, cycloaliphatic modified polycarconateresin, and acryloyl compound. Among the resins, resins having a Tg of120° C. or higher are preferred, and specific examples include filmscomprising a compound such as polyester resins, particularly, polyethylnaphthalate resin (PEN: 121° C.), polyarylate resin (PAr: 210° C.),polyether sulfone resin (PES: 220° C.), fluolene ring-modified carbonateresin (BCF-PC: a compound of Example 4 in JP-A 2000-227603: 225° C.),cycloaliphatic-modified polycarbonate resin (IP-PC: a compound ofExample 5 in JP-A No. 2000-227603: 205° C.), or an acryloyl compound (acompound of Example-1 in JP-A No. 2002-80616: 300° C.), etc. (the numberin each parenthesis represents Tg).

The present inventor has found that the constitution is particularlyeffective in a case when Tg of the substrate film is 120° C. or higher.Particularly, in a case of forming a film of silicon nitride by aninductively coupled plasma CVD, when the highest temperature in theprocess is monitored by adhering a thermo-tape on the surface of thesubstrate, it is observed to be 50° C. or lower in a case where a filmis formed on a resin substrate having different Tg value under utterlythe same condition, the barrier performance is extremely enhanced at Tgof about 100° C., and it is remarkably improved at Tg of 120° C. orhigher. Although the reason has not been analyzed sufficiently yet, itis estimated that this gives some effect on the state of the extremesurface that can not be detected by the thermo-tape.

The barrier property is preferred at 120° C., more preferred at 200° C.,further preferred, at 250° C. of Tg.

Further, as the compound constituting the substrate film, a resin havinga spiro structure represented by the following formula (1) or a resinhaving a cardo-structure represented by the following formula (2) ispreferred.

wherein a ring α represents a mononuclear or polynuclear ring and tworings may be identical or different with each other and are bonded byspiro bonding in the formula (1),

wherein a ring β and a ring γ each represents a mononuclear orpolynuclear ring, two rings γ may be identical or different with eachother and connected to one quaternary carbon on the ring β in formula(2).

Since the resin represented by the formula (1) or (2) is a compoundhaving high heat resistance, high modulus of elasticity and high tensilestress at break, it can be used suitably as a substrate material such asfor organic EL devices which are required for various kinds of heatingoperations in the production process and also required for lessfracturing performance even upon bending.

Examples of the ring α in the formula (1) include indane ring, chromanring, 2,3-dihydrobenzofuran ring, indoline ring, tetrahydropyran ring,tetrahydrofuran ring, dioxane ring, cyclohexane ring, cyclopentane ring,etc. Examples of the ring β in the formula (2) include a fluolene ring,indanedione ring, indanone ring, indene ring, indane ring, tetralonering, anthrone ring, cyclohexane ring, cyclopentane ring, etc. The ringγ in the formula (2) includes, for example, benzene ring, naphthalenering, anthracene ring, fluolene ring, cyclohexane ring, cyclopentanering, pyridine ring, furan ring, benzofuran ring, thiophene ring,benzothiophene ring, benzothiazole ring, indane ring, chroman ring,indole ring, and α-pyrone ring.

Preferred examples of the resin having a spiro structure represented bythe formula (1) includes a polymer containing a spirobiindane structurerepresented by the following formula (3) in the repetitive units, apolymer containing a spirobichromane structure represented by theformula (4) in the repetitive units, and a polymer containing aspirobibenzofuran structure represented by the formula (5) in therepetitive units.

In the formula (3), R³¹ and R³² each independently represents a hydrogenatom or a substituent. R³³ represents a substituent. Further, each ofR³¹, R³² and R³³ may bond to form a ring. m and n each independentlyrepresents an integer of from 0 to 3. Preferred examples of thesubstituent include a halogen atom, alkyl group, and aryl group. Furtherpreferably, R³¹ and R³² each independently represents a hydrogen atom,methyl group, or phenyl group. Further preferably, R³³ represents achlorine atom, bromine atom, methyl group, isopropyl group, tert-butylgroup, or phenyl group.

In the formula (4), R⁴¹ represents a hydrogen atom or a substituent. R⁴²represents a substituent. Further, each of R⁴¹ and R⁴² may bond to forma ring. m and n each independently represents an integer of from 0 to 3.Preferred examples of the substituent include a halogen atom, alkylgroup, and aryl group. R⁴¹ represents, further preferably, a hydrogenatom, methyl group, or phenyl group. R⁴² represents, further preferably,a chlorine atom, bromine atom, methyl group, isopropyl group, tert-butylgroup, or phenyl group.

In the formula (5), R⁵¹ represents a hydrogen atom or a substituent. R⁵²represents a substituent. Further, each of R⁵¹ and R⁵² may bond to forma ring. m and n each independently represents an integer of from 0 to 3.Preferred examples of the substituent include a halogen atom, alkylgroup, and aryl group. R⁵¹ represents, further preferably, a hydrogenatom, methyl group, or phenyl group. R⁵² represents, preferably, achlorine atom, bromine atom, methyl group, isopropyl group, tert-butylgroup or phenyl group.

The ring β in the formula (2) includes, for example, fluorene1,4-bibenzocyclohexane, and the ring γ includes, for example, phenylene,and naphthalene. The preferred examples of the resin having acardo-structure represented by the formula (2) include a polymercontaining a fluolene structure represented by the formula (6) in therepetitive units.

In the formula (6), R⁶¹ and R⁶² each independently represents asubstituent. Further, each of R⁵¹ and R⁵² may bond to form a ring. j andk each independently represents an integer of from 0 to 4. Preferredexamples of the substituent include a halogen atom, alkyl group, andaryl group. Further preferably, R⁵¹ and R⁵² each independentlyrepresents a chlorine atom, bromine atom, methyl group, isopropyl group,tert-butyl group, or phenyl group.

The resin containing the structure represented by the formulas (3) to(6) in the repetitive units may be a polymer which is bonded by variousbonding systems such as a polycarbonate, polyester, polyamide,polyimide, or polyurethane, and it is, preferably, a polycarbonate,polyester or polyurethane induced from a bisphenol compound having astructure represented by the formulae (3) to (6).

Preferred specific examples of the resin having a structure representedby the formula (1) or the formula (2) (resin compounds (I-1) to (FL-11))are described below. However, the resins which can be used in theinvention are not restricted to them.

The resins having a structure represented by the formula (1) and theformula (2) which can be used for the substrate film of the inventionmay be used alone, or may be used in admixture of several kinds of them.Further, they may be a homopolymer, or a copolymer of plural kinds ofstructures in combination. In a case of the resin of a copolymer, knownrepetitive units not containing the structure represented by the formula(1) or (2) in the repetitive units may be copolymerized within a rangenot impairing the effects of the invention. Preferably, the resincomprises a copolymer since it is after superior to a case of using aresin as a homopolymer with a view point of solubility and transparency.

A preferred molecular weight, on the basis of a weight average molecularweight, of the resin having the structures represented by the formulas(1) and (2) which can be used in the invention is preferably from 10,000to 500,000, preferably, from 20,000 to 300,000, and particularlypreferably from 30,000 to 200,000. In a case where the molecular weightof the resin is excessively low, film formation tends to be difficultand dynamic characteristics are sometimes deteriorated. On the contrary,in the case where the molecular weight is excessively high, themolecular weight is difficult to be controlled in view of synthesis, andthe handling of the solution is sometimes difficult because of itsexcessively high viscosity. The molecular weight can be roughlydetermined on the viscosity corresponding thereto.

It is preferred that the substrate film for use in the invention doesnot uptake water in view of the nature. That is, it is preferably formedof a resin having no hydrogen bonding functional group. The equilibriumwater content of the substrate film is, preferably, from 0.5 mass % orlower, further preferably, 0.1 mass % or lower and particularly,preferably, 0.05 mass % or less.

In a case of using a substrate film having a low equilibrium watercontent, electrostatic charging of the substrate film tends to occur.The electrostatic charging of the substrate film is an undesirablephenomenon since this causes adsorptive of particles to impair theproperties of the barrier layer, or causes handling failure due tobonding. Therefore, in order to solve the foregoing problems, it ispreferred that an antistatic layer is disposed on the surface of thesubstrate film in adjacent therewith.

The antistatic layer referred to herein is a layer in which the surfaceresistivity at 50° C. and 30% relative humidity is 1 Ω/□ to 10¹³ Ω/□.The surface resistivity of the antistatic layer at 50° C. and 30%relative humidity is, preferably, from 1×10⁸ Ω/□ to 1×10¹³ Ω/□, morepreferably, from 1×10⁸ Ω/□ to 1×10¹¹ Ω/□ and, particularly preferably,from 1×10⁸ Ω/□ to 1×10⁹ Ω/□.

Image Display Device

While the application use of the gas barrier film of the invention isnot particularly limited, since it is excellent in the opticalcharacteristics and mechanical characteristics, it can be used suitablyas a substrate for use in transparent electrodes of an image displaydevice. “Image display device” referred to herein means a circularpolarization plate, a liquid crystal display device, a touch panel, anorganic EL device, etc.

Circular Polarization Plate

The circular polarization plate can be manufactured by laminating a λ/4plate and a polarization plate on the gas barrier film of the invention.In this case, they are laminated such that the phase delay axis of theλ/4 plate and the absorption axis of the polarization plate form anangle of 45°. A polarization plate stretched in 45° direction relativeto the longitudinal direction (MD) is used preferably and, those, forexample, disclosed in JP-A No. 2002-865554 can be used suitably.

Liquid Crystal Display Device

A liquid crystal display device is generally classified into areflection type liquid crystal display device and a transmission typeliquid crystal display device.

The reflection type liquid crystal display device has a lower substrate,a reflection electrode, a lower orientation film, a liquid crystallayer, an upper orientation film, a transparent electrode, an uppersubstrate, a λ/4 plate, and a polarization film orderly from below. Thegas barrier film of the invention can be used as the transparentelectrode and the upper substrate. In a case of providing the reflectiontype liquid crystal display device with a color display function, acolor filter layer is preferably situated further between the reflectionelectrode and the lower orientation film, or between the upperorientation film and the transparent electrode.

Further, the transmission type liquid crystal display device has a backlight, a polarization plate, a λ/4 plate, a lower transparent electrode,a lower orientation film, a liquid crystal layer, an upper orientationfilm, an upper transparent electrode, an upper substrate, a λ/4 plate,and a polarization film orderly from below. Among them, the gas barrierfilm of the invention can be used as the upper transparent electrode andthe upper substrate. Further, in a case of providing the transmissiontype liquid crystal display device with the color display function, itis preferred that a color filter layer is preferably situated furtherbetween the lower transparent electrode and the lower orientation film,or between the upper orientation film and the transparent electrode.

While the structure of liquid crystal layer is not particularly limited,it is, preferably, for example, a TN (Twisted Nematic) type, an STN(Supper Twisted Nematic) type a HAN (Hybrid Aligned Nematic) type, a VA(Vertically Alignment) type, an ECB (Electrically ControlledBirefringence) type, an OCB (Optically Compensatory Bend) type, or a CPA(Continuous Pinwheel Alignment) type.

Touch Panel

As the tough panel, those applying the gas barrier film of the inventionto the substrate described, for example, in JP-A Nos. 5-127822 and2002-48913 can be used.

Organic EL Device

The organic EL device has a cathode and an anode on a gas barrier filmof the invention and has an organic compound layer containing an organiclight emitting layer (hereinafter sometimes simply referred to as “lightemitting layer”) between both of the electrodes. In view of the propertyof the light emitting device, at least one of the anode and the cathodeis preferably transparent.

As the mode of the lamination of the organic compound layer in theinvention, it is preferred such a mode where a hole transporting layer,a light emitting layer, and an electron transporting layer are laminatedin this order from the side of the anode. Further, a charge blockinglayer or the like may be present between the hole transporting layer andthe light emitting layer or between the light emitting layer and theelectron transporting layer. A hole injecting layer may be providedbetween the anode and the hole transporting layer and an electroninjecting layer may be present between the cathode and the electrontransporting layer. The light emitting layer may consist of only onelayer or the light emitting layer may be divided into a first lightemitting layer, a second light emitting layer, a third light emittinglayer, etc. Each of the layers may be divided into a plurality ofsecondary layers.

Constituent factors for an organic EL device of the invention is to bedescribed specifically.

Anode

It may usually suffice that the anode has a function as an electrode forsupplying holes to the organic compound layer and the shape, structure,size, etc. thereof are not particularly limited and can be selectedproperly from known electrode materials in accordance with theapplication use and the purpose of the light emitting device. Asdescribed above, the anode is formed usually as a transparent anode.

The material for the anode includes preferably, for example, metals,alloys, metal oxides, conductive compounds or mixtures of them. Specificexamples of the anode material include conductive metal oxides such astin oxide doped with antimony, fluorine, etc. (ATO, FTO), tin oxide,zinc oxide, indium oxide, indium tin oxide (ITO), and indium zinc oxide(IZO), metals such as gold, silver, chromium, and nickel, as well asmixtures or laminates of such metals with conductive metal oxides,inorganic conductive materials such as copper iodide, and coppersulfide, organic conductive materials such as polyaniline, polythiopheneand polypyrrole, and laminates thereof with ITO. Among them, preferredare conductive metal oxides, and ITO is particularly preferred with aview point of productivity, high conductivity, transparency, etc.

The anode can be formed on the substrate in accordance with a methodselected properly, for example, from wet method such as a printingmethod and a coating method, physical method such as a vacuum vapordeposition method, a sputtering method, and an ion plating method, andchemical method such as CVD or plasma CVD while considering theadaptability with the material constituting the anode. For example, in acase of selecting ITO as the material for the anode, the anode can beformed in accordance with a DC or RF sputtering method, a vacuumdeposition method, an ion plating method, etc.

In the organic EL device of the invention, the position for forming theanode is not particularly limited and can be selected properly inaccordance with the application use and the purpose of the lightemitting device and it is preferably formed on the substrate. In thiscase, the anode may be formed entirely or partially on one of thesurfaces of the substrate.

Patterning upon forming the anode may be conducted by chemical etchingadopting photolithography, etc., or by physical etching adopting laser,etc. Further, the patterning may be conducted by vapor deposition,sputtering, etc. while stacking a mask, or by a lift-off method or aprinting method.

The thickness of the anode can be selected properly depending on thematerial constituting the anode and, while it can not be determinedgenerally, it is usually about from 10 nm to 50 μm and, preferably, from50 nm to 20 nm.

The resistance value of the anode is, preferably, 10³ Ω/□ or less and,more preferably, 10² Ω/□ or less. In a case where the anode istransparent, it may be colorless transparent or colored transparent. Fortaking out light emission from the side of the transparent anode, thetransmittance is, preferably, 60% or higher and, more preferably, 70% orhigher.

The transparent electrode is described specifically in “New Developmentof Transparent Electrode Film”, supervised by Yutaka Sawada, publishedfrom CMC (1999) and the matters described therein can be applied to theinvention. In a case of using a plastic substrate of low heatresistance, a transparent electrode using ITO or IZO and formed as afilm at a low temperature of 150° C. or lower is preferred.

Cathode

It may usually suffice that the cathode has a function as an electrodefor injecting electrons to the organic compound layer and the shape,structure, size, etc. thereof are not particularly limited and can beselected properly from known electrode materials in accordance with theapplication use and the purpose of the light emitting device.

The material constituting the cathode includes, for example, metals,alloys, metal oxides, electroconductive compounds, and mixtures thereof.Specific examples include alkali metals (for example, Li, Na, K, andCs), group II metals (for example, Mg and Ca), gold, silver, lead,aluminum, sodium-potassium alloy, lithium-aluminum alloy,magnesium-silver alloy, indium, and rare earth metals such as ytterbium.They may be used alone or two or more of them can be preferably used incombination with a view point of making the stability and the electroninjecting property compatible.

Among them, as the material constituting the cathode, alkali metals orgroup II metals are preferred in view of the electron injecting propertyand materials mainly comprising aluminum are preferred with a view pointof excellent storage stability.

Materials mainly comprising aluminum mean aluminum per se, an alloy ofaluminum and from 0.01 to 10 mass % of an alkali metal or group IImetal, or a mixture thereof (for example, lithium-aluminum alloy, andmagnesium-aluminum alloy).

The materials for the cathode are described specifically in JP-A Nos.2-15595 and 5-121172 and the materials described in the publications canbe applied also to the invention.

The method of forming the cathode is not particularly limited and it canbe conducted in accordance with known methods. For example, the cathodecan be formed in accordance with a method selected properly from wettingmethod such as a printing method and a coating method, physical methodsuch as a vacuum vapor deposition method, a sputtering method or, an ionplating method, and chemical method such as a CVD or plasma CVD methodwhile considering the adaptability with the material constituting thecathode. For example, in a case of selecting metals or the like as amaterial for the cathode, it can be formed in accordance with asputtering method, etc. by sputtering one of them or plurality of themsimultaneously or successively.

Patterning upon forming the cathode may be conducted by chemical etchingsuch as photolithography, or physical etching such as by laser, or itmay be conducted by vacuum vapor deposition or sputtering while stackinga mask or by a lift off method or a printing method.

In the invention, the position for forming the cathode is notparticularly limited and it may be formed entirely or partially on theorganic compound layer.

Further, a dielectric layer of a fluoride or oxide of an alkali metal orgroup II metal may be inserted at a thickness of from 0.1 to 5 nmbetween the cathode and the organic compound layer. The dielectric layercan be regarded as a sort of an electron injecting layer. The dielectriclayer can be formed, for example, by a vacuum vapor deposition method, asputtering method or an ion plating method.

The thickness of the cathode can be selected properly depending on thematerial constituting the cathode and, while it can not be definedgenerally, it is usually about from 10 nm to 5 μm and, preferably, from50 nm to 1 μm.

The cathode may be transparent or not transparent. The transparentcathode can be formed by forming a thin film of the material of thecathode to a thickness of from 1 to 10 nm and, further, laminating atransparent conductive material such as ITO or IZO.

Organic Compound Layer

The organic compound layer in the invention is to be described.

The organic EL device of the invention has at least one organic compoundlayer containing at least a light emitting layer. Other organic compoundlayers than the organic light emitting layer include layers such as ahole transporting layer, an electron transporting layer, a chargeblocking layer, a hole injecting layer, and an electron injecting layerrespectively as described above.

-Formation of Organic Compound Layer-

In the organic EL device of the invention, each of the layersconstituting the organic compound layer can be formed suitably by any ofa dry film forming method such as a vapor deposition method or asputtering method, a transfer method, a printing method, etc.

-Organic Light Emitting Layer-

The organic light emitting layer is a layer having a function ofaccepting holes from the anode, the hole injecting layer, or the holetransporting layer and accepting electrons from the cathode, theelectron injecting layer, or the electron transporting layer uponapplication of an electric field, and providing a site forre-combination of hole and electron to emit light.

The light emitting layer in the invention may be formed only of a lightemitting material, or may be formed of a mixture of a host material andlight emitting material. The light emitting material may a fluorescenceemitting material or a phosphorescence emitting material and the dopantmay be of one or plural kinds. The host material is preferably a chargetransportable material. The host material may be of one or plural kindsand includes, for example, a mixture of an electron transporting hostmaterial and a hole transporting host material. Further, it may alsocontain a material not having charge transportability and not emittinglight in the light emitting layer.

Further, the light emitting layer may have one or more layers and eachof the layers may emit light at different emission colors.

In the invention, a light emitting device of any desired color can beobtained by using two or more kinds of light emitting materialsdifferent from each other. Among them, a white light-emitting device athigh emission efficiency and high emission brightness can be obtained byproperly selecting the light emitting materials. For example, whitelight can be emitted by using light emitting materials that emit lightsof colors in a complementary relation such as blue light emission/yellowlight emission or, aqua color light emission/orange light emission,green light emission/purple light emission. Further, white lightemission can be obtained by using light emitting materials of blue lightemission/green light emission/red light emission.

The host material may emit light also having a function of the lightemitting material. For example, the device may be caused to emit whitelight by the emission of the host material and the emission of the lightemitting material.

In the invention, two or more different kinds of light emittingmaterials may be contained in one identical light emitting layer.Alternatively, a structure of laminating layers containing respectivelight emitting materials, for example, as blue light emittinglayer/green light emitting layer/red right emitting layer, or blue lightemitting layer/yellow light emitting layer may be adopted.

The method of adjusting the emission color of the light emitting layermay also include the followings. The emission color can be adjusted byusing one or plurality of such methods.

-   (1) Adjusting method by providing a color filter on the side of    taking out light from the light emitting layer

A color filer adjusts the emission color by restricting transmittingwavelength. As the color filter, known materials may be used such ascobalt oxide for the blue filter, a mixed system of cobalt oxide andchromium oxide for the green filter, and iron oxide for the red filter,which may be formed on a transparent substrate by using known thin filmforming method, for example, a vacuum vapor deposition method.

-   (2) A method of adjusting emission color by addition of a material    of promoting or inhibiting emission

For example, a so-called assistant dopant of accepting energy from ahost material and transferring the energy to the light emitting materialcan be added to facilitate energy transfer from the host material to thelight emitting material. The assistant dopant is properly selected fromknown materials and, for example, selected sometimes from materials thatcan be utilized as the light emitting material or the host material tobe described later.

-   (3) A method of adjusting emission color by adding a material for    converting wavelength to the layer (including a transparent    substrate) on the side of taking out light from the light emitting    layer

As the material, known wavelength conversion material can be used and,for example, a fluorescence conversion substance of converting a lightemitted from a light emitting layer to other light of low energywavelength can be adopted. The kind of the fluorescence conversionmaterial is properly selected in accordance with the wavelength of alight to be emitted from an aimed organic EL device and a wavelength oflight emitted from the light emitting layer. Further, the amount of thefluorescence conversion substance to be used can be selected properly inaccordance with the kind thereof within a range not causing densityextinction. As the fluorescence conversion substance, only one kind ofthe substance may be used or a plurality kinds of substances may be usedin combination. In a case of using plural species in combination, whitelight or intermediate color light can also be emitted in addition to theblue light, green light, and red light depending on the combination.

Examples of the fluorescence emitting material usable in the inventioninclude, for example, various metal complexes typically represented bymetal complexes of benzoxazole derivatives, imidazole derivatives,benzothiazole derivatives, styrylbenzene derivatives, polyphenylderivatives, diphenyl butadiene derivatives, tetraphenyl butadienederivatives, naphthalimide derivatives, coumarine derivatives, condensedaromatic compound, perynone derivatives, oxadiazole derivatives, oxazinederivatives, aldazine derivatives, pyralidine derivatives,cyclopentadiene derivatives, bisstyryl anthracene derivatives,quinacridone derivatives, pyrrolopyridine derivatives,thiadiazolopyridine derivatives, cyclopentadiene derivatives,styrylamine derivatives, diketopyrrolopyrole derivatives, aromaticdimethylidene compound, and 8-quinolinole derivatives, and metalcomplexes of pyrrometene derivatives, polymer compounds such aspolythiophene, polyphenylene and compounds such as polyphenylenevinylene, and organic silane derivatives.

Further, the phosphorescence emitting materials usable in the inventionincludes, for example, complexes containing transition metal atoms orlanthanoide atoms.

The transition metal atoms are not particularly limited and include,preferably, ruthenium, rhodium, palladium, tungsten, rhenium, osmium,iridium, and platinum and, more preferably, rhenium, iridium andplatinum.

The lanthanoide atoms include lanthanum, cerium, praseodymium,neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium,erbium, thulium, ytterbium, and lutetium. Among the lanthanoide atoms,neodymium, europium, and gadolinium are preferred.

Ligands of complexes include those ligands, described, for example, in“Comprehensive Coordination Chemistry”, written by G. Wilkinson, et al.,published from Pergamon Press in 1987, “Photochemistry and Photophysicsof Coordination Compounds” written by H. Yersin, published fromSpringer-Verlag Co. in 1987, and “Organic Metal Chemistry—Foundation andApplication—” written by Akio Yamamoto, published from Shokabo Co. in1982, etc.

Specific ligands are, preferably, halogen ligands (preferably, chlorineligand), nitrogen-containing heterocyclic ligands (for example,phenylpyridine, benzoquinoline, quinolinol, bipyridyl, andphenanthroline), diketone ligands (for example, acetylacetone),carboxylic acid ligands (for example, acetic acid ligand), carbonmonoxide ligand, isonitrile ligand, and cyano ligand and, morepreferably, nitrogen-containing heterocyclic ligands. The complexesdescribed above may have one transition metal atom in the compound ormay be a so-called composite nuclei complexes having two or more ofthem. Metal atoms of different kinds may be contained together.

The phosphorescence emitting material is contained in the light emittinglayer by, preferably, from 0.1 to 40 mass % and, more preferably, from0.5 to 20 mass %.

Further, the host materials contained in the light emitting layer in theinvention include, for example, those having carbazole skeleton, havingdiarylamine skeleton, having pyridine skeleton, having pyrazineskeleton, having triazine skeleton, and having arylsilane skeleton, orthose materials exemplified in the columns for the hole injecting layer,the hole transporting layer, the electron injecting layer and theelectron transporting layer to be described later.

The thickness of the light emitting layer is not particularly limitedand usually it is, preferably, from 1 nm to 500 nm, more preferably,from 5 nm to 200 nm and, further preferably, from 10 nm to 100 nm.

-Hole Injecting Layer, Hole Transporting Layer-

The hole injecting layer and the hole transporting layer are layershaving a function of accepting holes from the anode or from the side ofthe anode and transporting them to the cathode. The hole injecting layerand the hole transporting layer are preferably layers containingspecifically, for example, carbazole derivatives, triazole derivatives,oxazole derivatives, oxadiazole derivatives, imidazole derivatives,polyarylalkane derivatives, pyrazoline derivatives, pyrazolonederivatives, phenylenediamine derivatives, arylamine derivatives,amino-substituted chalcone derivatives, styrylanthracene derivatives,fluorenone derivatives, hydrazone derivatives, stylbene derivatives,silazene derivatives, aromatic tertiary amine compounds, styrylaminecompounds, aromatic dimethylidine compounds, porphiline compounds,organic silane derivatives, and carbon.

The thickness of the hole injecting layer and the hole transportinglayer is preferably each 500 nm or less with a view point of loweringthe driving voltage.

The thickness of the hole transporting layer is, preferably, from 1 nmto 500 nm, more preferably, from 5 nm to 200 nm and, further preferably,from 10 nm to 100 nm. Further, the thickness of the hole injecting layeris, preferably, from 0.1 nm to 200 nm, more preferably, from 0.5 nm to100 nm and, further preferably, from 1 nm to 100 nm.

The hole injecting layer and the hole transporting layer may be of asingle layered structure comprising one or more of the materialsdescribed above or may be of a multi-layered structure comprising plurallayers of an identical composition or different kinds of compositions.

-Electron Injecting Layer, Electron Transporting Layer-

The electron injecting layer and the electron transporting layer arelayers having a function of accepting electron from the cathode or fromthe side of the cathode and transporting them to the side of the anode.The electron injecting layer and the electron transporting layer arepreferably layers containing, specifically, various kinds of metalcomplexes typically represented by metal complexes of triazolederivatives, oxazole derivatives, oxodiazole derivatives, imidazolederivatives, fluorenone derivatives, anthraquinodimethane derivatives,anthron derivatives, diphenylquinone derivatives, thiopyrane dioxidederivatives, carbodiimide derivatives, fluorenylidene methanederivatives, distyrylpyradine derivatives, aromatic ring tetracarboxylicacid anhydrides such as naphthalene and perylene, phthalocyaninederivatives, and 8-quinolinole derivatives, and metal complex havingmetal phthalocyanine, benzoxazole, or benzothiazole as the ligand,organic silane derivatives, etc.

The thickness of the electron injecting layer and the electrontransporting layer is preferably from 500 nm or less respectively with aview point of lowering the driving voltage.

The thickness of the electron transporting layer is, preferably, from 1nm to 500 nm, more preferably, from 5 nm to 200 nm and, furtherpreferably, from 10 nm to 100 nm. Further, the thickness of the electroninjecting layer is, preferably, from 0.1 nm to 200 nm, more preferably,from 0.2 nm to 100 nm and, further preferably, from 0.5 nm to 50 nm.

The electron injecting layer and the electron transporting layer may beof a single layered structure comprising one or more of the materialsdescribed above or a multi-layered structure comprising plural layerseach of an identical composition or different kinds of compositions.

Further, for moderating the energy barrier between the cathode and thelight emitting layer, an alkali metal or an alkali metal compound may bedoped to the layer adjacent the cathode. Since the organic layer isreduced by the added metal or metal compound to form anions, theelectron injecting property is enhanced and the application voltage islowered. The alkali metal compound includes, for example, oxides,fluorides and lithium chelates.

-Hole Blocking Layer-

The hole blocking layer is a layer having a function of preventing holestransported from the anode to the light emitting layer from passingthrough to the side of the cathode. In the invention, the hole blockinglayer can be provided as an organic compound layer adjacent with thelight emitting layer on the side of the cathode. The electrontransporting layer or the electron injecting layer may also have afunction of the hole blocking layer.

Examples of the organic compound constituting the hole blocking layerinclude aluminum complexes such as BAl_(q), triazole derivatives, andphenanthroline derivatives such as BCP.

The thickness of the hole blocking layer is, preferably, from 1 nm to500 nm, more preferably, 5 nm to 200 nm and, further preferably, from 10nm to 100 nm.

The hole blocking layer may be of a single layered structure comprisingone or more kinds of the materials described above or a multi-layeredstructure comprising plural layers each of an identical composition ordifferent kinds of compositions.

Further, a layer having a function of preventing electrons transportedfrom the side of the cathode to the light emitting layer from passingthrough to the side of the anode may also be situated at a positionadjacent with the light emitting layer on the side of the anode. Thehole transporting layer or the hole injecting layer may also have suchfunction together.

Protective Layer

In the invention, the entire organic EL device may be protected by aprotective layer.

The material contained in the protective layer may be any material ofsuppressing intrusion of moisture or oxygen into the device thatpromotes deterioration of the device.

Specific examples include metals such as In, Sn, Pb, Au, Cu, Ag, Al, Ti,and Ni, metal oxides such as MgO, SiO, SiO₂, Al₂O₃, GeO, NiO, CaO, BaO,Fe₂O₃, Y₂O₃, and TiO₂, metal nitrides such as SiN_(x), SiN_(x)O_(y),metal carbides such as SiC_(w) and SiO_(z)C_(w), metal fluorides such asMgF₂, LiF, AlF₃, and CaF₂, polyethylene, polypropylene, polymethylmethacrylate, polyimide, polyurea, polytetrafluoroethylene,polychlorotrifluoroethylene, polydichlorodifluoroethylene, copolymer ofchlorotrifluoroethylene and dichlorofluouroethylene, a copolymerobtained by copolymerizing tetrafluoroethylene and a monomer mixturecontaining at least one comonomer, a fluoro-containing copolymer havinga cyclic structures in the copolymerization main chain, water absorbingmaterial with a water absorptivity of 1% or more, and a moistureproofing material with a water absorptivity of 0.1% or less.

The method of forming the protective layer is not particularly limitedand, for example, a vacuum vapor deposition method, a sputtering method,a reactive sputtering method, an MBE (Molecular Beam Epitaxy) method, acluster ion beam method, an ion plating method, a plasma polymerizationmethod (RF-excited ion plating method), a plasma CVD method, a laser CVDmethod, a thermal CVD method, a gas source CVD method, a coating method,a printing method, or a transfer method can be applied.

Sealing

Further, the organic EL device of the invention may be sealed for theentire device by using a sealing vessel.

Further, a water absorbent or an inert liquid may be sealed in a spacebetween the sealing vessel and the light emitting device. The waterabsorbent is not particularly limited and includes, for example, bariumoxide, sodium oxide, potassium oxide, calcium oxide, sodium sulfate,calcium sulfate, magnesium sulfate, phosphorous pentoxide, calciumchloride, magnesium chloride, copper chloride, cesium fluoride, niobiumfluoride, calcium bromide, vanadium bromide, molecular sieve, zeolite,and magnesium oxide. The inert liquid is not particularly limited andincludes, for example, paraffins, liquid paraffins, fluoro-solvents suchas perfluoro alkanes or perfluoro amines and perfluoro ethers,chloro-solvents, and silicone oils.

Light emission can be obtained from the organic EL device of theinvention by applying a DC (may optionally containing AC component)voltage (usually from 2 to 15 V), or a DC current between the anode andthe cathode.

For the driving method of the organic EL device of the invention, adriving method described in each of the publications of JP-A Nos.2-148687, 6-301355, 5-29080, 7-134558, 8-234685 and 8-241047, and ineach of the specifications of JP No. 2784615, and U.S. Pat. Nos.5,828,429 and 6,023,308 can be applied.

In a case of using the gas barrier film of the invention for the organicEL device, it may be used as a substrate film and/or protective film.

Further, the gas barrier laminate disposed to the substrate film of theinvention may be disposed on the device instead of the substrate filmfor sealing. In the invention, after forming the film of the organic ELdevice, it is preferred to dispose at least one three-layer unitconsisting of a silicon nitride layer, a silicon carbide compound layer,and a silicon nitride layer arranged orderly adjacent with each other invacuum without exposure to atmospheric air. Preferred film thickness,composition and constitution are in common with those of the gas barrierlayer, which may be identical or different.

EXAMPLE

The present invention will be further specifically explained withreference to the following examples of the present invention. Thematerials, amounts, ratios, types and procedures of treatments and soforth shown in the following examples can be suitably changed unlesssuch changes depart from the gist of the present invention. Accordingly,the scope of the present invention should not be construed as limited tothe following specific examples.

Example 1

Gas barrier films each formed by disposing a gas barrier laminate on asubstrate film and a transparent conductive layer thereon (Specimen Nos.1 to 21) were prepared in accordance with the following procedures.Details for the structure of each of the gas barrier films are asdescribed in Table 1 and Table 2.

Preparation of Gas Barrier Films of the Invention (Specimens Nos. 1 to17)

(1) Preparation of Substrate Film

Substrate films of 100 μm thickness comprising resins described in Table1 were provided. In Table 1, Lumilar T60 manufactured by Toray Co. wasused as PET, and Teonex Q65AF manufactured by Teijin Dupont Film Co. wasused as PEN. Further, the substrate films used for Specimens Nos. 8 to14 were prepared from the resins as the starting materials by thefollowing method.

The resin was dissolved in a dichloromethane solution such that theconcentration was 15 mass % and the solution was cast by a die coatingmethod over a stainless steel band. Then, the first film was peeled fromthe band and dried till the residual solvent concentration was 0.08 mass%. After drying, both ends of the first film were trimmed, applied withknurling fabrication and then taken-up to prepare a substrate film of100 μm thickness.

(2) Formation of Gas Barrier Laminate

An inorganic gas barrier layer was formed on a substrate film by using aroll-to-roll system inductively coupled plasma CVD apparatus (1) shownin FIG. 1. As shown in FIG. 1, the induction-coupled plasms CVDapparatus (1) has a vacuum vessel (2), in which a drum (3) is located ata central portion thereof for cooling a plastic film (6) by contact atthe surface. A delivery roll (4) and a take-up roll (5) for winding theplastic film (6) are arranged in the vacuum vessel (2). The plastic film(6) wound around the delivery roll (4) is wound by way of a guide roll(7) to the drum (3) and, further, the plastic film (6) is wound by wayof the guide roll (8) to the take-up roll (5). In a vacuum exhaustionsystem, the inside of the vacuum vessel (2) is always exhausted by avacuum pump (10) from exhaust ports (9). The film forming systemcomprises an RF power source (11) having induction coils for generatinginduction electric fields connected with an auto-matcher, a gasintroduction system for a gas source for introducing a gas of apredetermined flow rate from a reservoir by way of a gas flow ratecontrol unit (14) and a pipe line (15) for gas source, and a gasintroduction system for introducing a vapor at a predetermined flow ratefrom a liquid source reservoir tank (17) for evaporating a liquid sourceby setting a predetermined temperature by a thermostable tank (18) andthrough a gas flow rate control unit (14) and a temperature keepingjacketed pipeline (for liquid source) (16).

Specific conditions during formation of the inorganic gas barrierlaminate are shown below.

The substrate film was disposed as the plastic film (6), which was puton the delivery roll (4) and passed as far as the take-up roll (5).After completing the preparation of the substrate to the inductivelycoupled plasma CVD apparatus (1), a door for the vacuum vessel (2) wasclosed, the vacuum pump (10) was actuated and evacuation was started.When the pressure reached 4×10⁻⁴ Pa, running of the plastic film (6) wasstarted. Argon was introduced as a discharge gas and the dischargingpower source (11) was turned-ON and RF at 13.56 MHz was applied at adischarging power of 500 W to generate plasmas in the vacuum vesselunder a film forming pressure described in Table 1 and Table 3 andplasma cleaning treatment was conducted for 5 min. Then, a silane gasdiluted to 5% with nitrogen was introduced as a reaction gas and, afterconfirming the stabilization of discharge under the film formingpressure, the film transporting direction was reversed and formation ofa silicon nitride film was conducted for a certain time. Aftercompletion of the film formation, the silicon carbide compound wasintroduced slowly and, after confirming the stabilization of discharge,the film was transported in the direction opposite to that describedabove to form a film of silicon carbide. The kind and the flow rate ofthe silicon carbide compound were as described in Table 1 and Table 3.Then, introduction of the silicon carbide compound was interrupted and asilane gas diluted with nitrogen to 5% was introduced, the film wastransported again in the opposite direction under the same condition asthat for the first layer to form a film of the silicon nitride layer.When the refractive index of the obtained silicon nitride layer wasmeasured (“WOOLLAM-VASE”, manufactured by Woollam Japan Co.), it wasfrom 2.0 to 2.1 for each of the specimens. Further, when the atomconstituent ratio Si:N in the obtained silicon nitride layer wasmeasured (measured while etching by using “ESCA 3400”, manufactured byClaitos Analytical Co.), it was 1:1.30 to 1.35.

(3) Formation of Transparent Conductive Layer

The specimens obtained as described above were introduced into a vacuumchamber of a commercially available batch type magnetron sputteringapparatus (manufactured by Shibaura Mechatronics Co.), and the anode ofindium tin oxide (ITO, indium/tin=95/5 molar ratio) was formed (0.2 μmthickness) by using a DC power source.

As described above, the gas barrier films of the invention (SpecimensNos. 1 to 17) were obtained.

Preparation of Gas Barrier Films for Comparison (Specimen No. 18)

A gas barrier film for comparison (Specimen No. 18) was prepared quitein the same manner as in the manufacturing steps for the Specimen No. 2except for not conducting the step of forming the silicon carbidecompound layer in the preparation step for the Specimen No. 2. Therefractive index of the silicon nitride layer was 2.06. The atomic ratioSi:N was 1:1.32. Preparation of gas barrier films for comparison(Specimen No. 19)

A comparative gas barrier film (Specimen No. 19) was prepared quite inthe same manner as in the preparation step for Specimen No. 2 except fornot practicing the step of forming the silicon nitride layer nearer tothe substrate film in the preparation step for Specimen No. 2 andsetting the thickness of the gas barrier film (Specimen No. 19) to 100nm. The refractive index of the silicon nitride layer was 2.05. Theatomic ratio Si:N was 1:1.33.

Preparation of Gas Barrier Film for Comparison (Specimen Nos. 20, 21)

1. Formation of Inorganic Layer

A roll-to-roll system sputtering apparatus (1) as shown in FIG. 2similar with that of FIG. 1 was used. The apparatus has a vacuum vessel(2) in which a drum (3) is located at a central portion thereof forcooling a plastic film (6) by contact at the surface. A delivery roll(4) and a take-up roll (5) for winding the plastic film (6) are arrangedin the vacuum vessel (2). The plastic film (6) wound around the deliveryroll (4) is wound by way of a guide roll (7) to the drum (3) and,further, the plastic film (6) is wound by way of the guide roll (8) tothe take-up roll (5). In a vacuum exhaustion system, the inside of thevacuum vessel (2) is always exhausted by a vacuum pump (10) from exhaustports (9). As the film formation system, a target (not illustrated) ismounted on a cathode (12′) connected to a DC system discharge powersource (11′) that can supply pulsed power. The discharge power source(11′) is connected to a controller (13) and, further, the controller(13) is connected to the gas flow rate control unit (14) for supplyingthe gas while controlling the amount of the reaction gas introduced byway of a pipeline (15) to the vacuum vessel (2). Further, it is adaptedsuch that a discharge gas at a predetermined flow rate is supplied tothe vacuum vessel (2) (not illustrated). Specific conditions are shownbelow.

Si was set as a target, and a pulse application type DC power source wasprovided as the discharging power source (11′). The same substrate film(PEN film) as used for the preparation of Specimen No. 2 was provided asthe plastic film (6), which was put on the delivery roll (4) and passedas far as the take-up roll (5). After completing the preparation of thesubstrate to the sputtering apparatus (1), a door for the vacuum vessel(2) was closed and the vacuum pump (10) was actuated and evacuation andthe drum cooling were started. When the pressure reached 4×10⁻⁴ Pa andthe drum temperature was cooled to 5° C., running of the plastic film(6) was started. Argon was introduced as the discharging gas and thedischarging power source (11′) was turned-ON to generate plasmas abovethe Si target with a discharging power of 5 KW and a film-formingpressure of 0.3 Pa, and pre-sputtering was conducted for 3 min.Subsequently, oxygen was introduced as a reaction gas and the amount ofargon and oxygen gas was gradually decreased to lower the film-formingpressure to 0.1 Pa after the discharging was stabilized. Afterconfirming the stabilization of discharging at 0.1 Pa, formation of asilicon oxide film was conducted for a predetermined time. Aftercompleting the film formation, inside of the vacuum vessel (2) wasreturned to the atmospheric pressure and a film deposited with siliconoxide was taken out. The thickness was about 50 nm.

2. Formation of Organic Layer

Then, an acrylic monomer mixture of 50.75 mL of tetraethylene glycoldiacrylate, 14.5 mL of tripropylene glycol monoacrulate, 7.25 mL ofcaprolacton acrylate, 10.15 mL of acrylic acid, and 10.15 mL of“SarCure” (photopolymerization initiator of benzophenone mixturemanufactured by Sartomer Co.) was mixed with 36.25 g of solidN,N′-bis(3-methylphenyl)-N,N′-diphenylbenzidine particles, and stirredfor about one hour by a supersonic tissue mincer at 20 kHz. They wereheated to about 45° C. and the mixture stirred for preventing settlingwas sent by a pump through a capillary of 2.0 mm inner diameter and 61mm length to a 1.3 mm spray nozzle. Then, it was sprayed as finedroplets by a supersonic sprayer at 25 kHz and dropped to the surfacemaintained at about 340° C. Then, after cryogenically condensing steamson the substrate film in contact with a low temperature drum at atemperature of about 13° C., it was UV-cured by a high pressure mercurylamp (accumulated amount of irradiation: about 2000 mJ/cm²) to form anorganic layer. The film thickness was about 500 nm.

3. Alternate Repetitive Film Formation of Inorganic LayerFormation/Organic Layer Formation, and Formation of TransparentConductive Layer

A gas barrier laminate was prepared by repeating the procedures (1) and(2) above, and then disposing an inorganic layer (SiO_(x) layer)similarly to (1) (3 layers in total) . Then, a gas barrier film forcomparison (Specimen No. 20) was obtained by applying the steps offorming the conductive transparent layer practiced in the preparation ofSpecimen No. 8 described above.

A gas barrier film for comparison (Specimen No. 21) was obtained in thesame manner as in Specimen No. 20 except for laminating inorganiclayers/organic layers by conducting the procedures (1) and (2) each bythree times alternately between the organic layer and the SiO_(x) layerprepared in (2) above in the steps of preparing the Specimen No. 20.

Evaluation for Physical Property of Barrier Film

The physical properties of the barrier film were evaluated by using thefollowing apparatus.

-   -   Layer constitution (film thickness): scanning type electron        microscope “model S-900”, manufactured by Hitachi Ltd.    -   Steam permeability (g/m².day): “PERMATRAN-W3/31”, manufactured        by MOCON Co. (condition: 40° C. 90% RH)    -   Atomic ratio: “ESCA 3400”, manufactured by Claitos Analytical        Co.

Example 2

Manufacture of Organic EL Device (I)

An anode of an indium tin oxide (ITO, indium/tin=95/5 molar ratio) wasformed on a gas barrier film of 25 mm×25 mm (Specimens Nos. 1 to 21)using a DC power source by a sputtering method (0.2 μm thickness),copper phthalocyanine (CuPc) was formed as a hole injecting layer to 10nm on the anode by a vacuum vapor deposition method, on whichN,N′-dinaphthyl-N,N′-diphenyl benzidine was formed as the holetransporting layer to 40 nm by a vacuum deposition method.4,4′-N,N′-dicarbazole biphenyl as the host material,bis[(4,6-difluorophenyl)-pyridinate-N, C2′] (picolinate) iridium complex(Firpic) as the blue color emitting material, tris(2-phenylpyridine)iridium complex (Ir(ppy)₃) as the green color emitting material, andbis(2-phenylquinoline) acetyl acetonate iridium as the red lightemitting material were co-vapor deposited over them at a weight ratio of100/2/4/2 respectively, to obtain a light emitting layer of 40 nm.Further, 2,2′,2″-(1,3,5-benzenetoluyl)tris[3-(2-methylphenyl)-3H-imidazo[4,5-b]pyridine] was vapordeposited as the electron transporting material thereon at a rate of 1nm/sec to form an electron transporting layer of 24 nm. A patterned mask(a mask providing a light emission area of 5 mm×5 mm) was placed on theorganic compound layer, and lithium fluoride was vapor deposited to 1 nmand, further, aluminum was vapor deposited to 100 nm in a vapordeposition apparatus to form a cathode. Aluminum lead wires were led outof the anode and the cathode respectively to prepare a light emittingdevice. The device was placed in a globe box replaced with a nitrogengas sealed with a glass cap and UV-ray curable adhesive (XNR5493,manufactured by Nagase Chiba) to manufacture a light emitting device.

Manufacture of Organic EL Device (II)

After preparing the light emitting devices in the same manner as in themanufacture of the organic EL devices (I) by using the gas barrier films(Specimen Nos. 1 to 21), sealing was conducted quite under the sameconditions with those for the constitution of the barrier layer on thecorresponding substrate film instead of sealing by the glass cap.

Bending Resistance Test; Manufacture of Organic EL Device (III)

Organic EL devices (III) were manufactured in the same manner as in theEL device (I) described above except for using substrate cutting a gasbarrier film to 30 mm×200 mm and respectively to a state of bending (180degree) and a state of not-bending for 100 times with the barrier facebeing outside on a cylinder of 16 mm diameter by using a bending tester“Cylindrical Mandrel Method Type I” manufactured by Coating TesterIndustry Co.

Durability Test for Organic EL Devices (I)-(III)

When a DC current was applied to the organic EL devices (I) to (III)obtained as described above using a source measure unit model 2400(manufactured by Toyo Technica Co.) to emit light, each of the devicesemitted light satisfactorily.

Then, after preparing the organic EL devices, they were left at 60°C.·90% RH for 500 hours to emit light in the same manner, and the areaof the light emitting portion for the entire device (not-light emittingportion: dark spot) was determined by using a micro analyzermanufactured by Nippon Poladigital Co.

Results of Examples 1 and 2 are collectively shown in Table 1.

TABLE 1 Substrate film Silicon carbide Glass transition compound layerSi:C:O in Steam Specimen temperature Film forming silicon carbidepermeability No. Kind Resin (° C.) Structure condition compound layer(g/m² · d)  1 a PET 77 A i 10:2.1:4.1 <0.01(*)  2 b PEN 121 A i10:2.1:4.2 <0.01(*)  3 b PEN 121 A ii 10:8.3:16.1 <0.01(*)  4 b PEN 121A iii 10:1.1:2.1 <0.01(*)  5 b PEN 121 A iv 10:1.9:3.9 <0.01(*)  6 b PEN121 A v 10:2.0:4.2 <0.01(*)  7 b PEN 121 A vi 10:2.0:4.1 <0.01(*)  8 c1-1 224 A i 10:2.1:4.1 <0.01(*)  9 d 1-5 214 A i 10:2.1:4.2 <0.01(*) 10e F-3 279 A i 10:2.1:4.1 <0.01(*) 11 f H-8 280 A i 10:1.9:4.1 <0.01(*)12 g FL-1 324 A i 10:2.0:4.0 <0.01(*) 13 g FL-1 324 A iv 10:7.7:15.2<0.01(*) 14 g FL-1 324 A v 10:1.0:2.1 <0.01(*) 15 b PEN 121 A vii10:12.5:11.0 <0.01(*) 16 b PEN 121 A viii 10:0.9:1.8 <0.01(*) 17 b PEN121 A ix 10:0:1.2 <0.01(*) 18 b PEN 121 B — — <0.01(*) 19 b PEN 121 C —10:2.1:4.1 0.08 20 b PEN 121 D — — 0.07 21 b PEN 121 E — — <0.01(*)Emission area ratio of organic EL device at Number of 60° C., 90% RHafter lapse of 500 hours windings in Specimen Organic EL Organic ELOrganic EL specimen No. device (I) device (II) device (III) preparationRemarks  1 65% 64% 65% 3 times Invention  2 92% 90% 91% 3 timesInvention  3 86% 81% 85% 3 times Invention  4 85% 82% 85% 3 timesInvention  5 88% 86% 87% 3 times Invention  6 93% 89% 92% 3 timesInvention  7 92% 89% 92% 3 times Invention  8 95% 93% 94% 3 timesInvention  9 96% 94% 96% 3 times Invention 10 97% 95% 97% 3 timesInvention 11 98% 97% 97% 3 times Invention 12 100%  100%  100%  3 timesInvention 13 98% 96% 97% 3 times Invention 14 96% 95% 96% 3 timesInvention 15 48% 45% no emission 3 times Invention 16 20% 17% noemission 3 times Invention 17 35%  8% no emission 3 times ComparativeExample 18 10% no emission no emission Twice Comparative Example 19 16%no emission no emission Twice Comparative Example 20 18% no emission noemission 3 times Comparative Example 21 94% 89% 88% 5 times ComparativeExample (*)less than detection limit

TABLE 2 Structure Content of structure: ( ) shows thickness A Substratefilm/SiN_(x) (100 nm)/Si_(y)O_(z)C_(w) (500 nm)/ SiN_(x) (100 nm) BSubstrate film/SiN_(x) (100 nm)/SiN_(x) (100 nm) C Substratefilm/Si_(y)O_(z)C_(w) (100 nm)/SiN_(x) (100 nm) D Substrate film/SiO_(x)(50 nm)/organic layer (500 nm)/SiO_(x) (50 nm) E Substrate film/{SiO_(x)(50 nm)/organic layer (500 nm)} × 4/SiO_(x) (50 nm) *“SiN_(x)”,“Si_(y)O_(z)C_(w)” each represents silicon nitride and silicon carbidecompound.

As apparent from the result of Table 1, the gas barrier film of theinvention (Specimens Nos. 1 to 17) can provide highly durable organicelectrolumiscence device compared with gas barrier films for comparison(Specimens Nos. 18 to 19).

Further, Specimens Nos. 2, 8 to 12 manufactured under the same processconditions using film substrates comprising constituent resins havinghigher glass transition temperature can provide organicelectroluminescence devices of higher durability, when compared withSpecimen No. 1. Further, among them, Specimens Nos. 8 to 14 usingsubstrate films comprising resins having specified spiro structures orpolymers having specified cardo structures described in the inventioncan provide organic electroluminescence devices of further higherdurability.

Further, Specimens Nos. 2 to 7 with the conditions that the ratiobetween silicon atom and carbon atom in the silicon carbide compoundlayer is from 1:1 to 10:1 can provide organic electroluminescencedevices of further higher durability, when compared with Specimens Nos.15 to 17.

On the other hand, the gas barrier films (Specimens Nos. 1 to 17) of theinvention can remarkably decrease the number of roll windings duringmanufacture, when compared with the gas barrier film (Specimen No. 21)for comparison (by the way Specimen No. 20 of identical number ofwinding can provide only those of apparently poor performance). That is,the invention can provide films of higher gas barrier property by themanufacturing method at high productivity.

Since the gas barrier film of the invention has excellent transparencyand gas barrier property, it can be used suitably as substrates forvarious kinds of devices and coating films for devices. Further, thesubstrate for use in the image display device and the organic EL deviceof the invention have high bending resistance and durability capable ofproviding flexibility and have high productivity compared to relatedart. Accordingly, the invention has high industrial applicability.

The present disclosure relates to the subject matter contained inJapanese Patent Application No. 114574/2005 filed on Apr. 12, 2005,which is expressly incorporated herein by reference in its entirety.

The foregoing description of preferred embodiments of the invention hasbeen presented for purposes of illustration and description, and is notintended to be exhaustive or to limit the invention to the precise formdisclosed. The description was selected to best explain the principlesof the invention and their practical application to enable othersskilled in the art to best utilize the invention in various embodimentsand various modifications as are suited to the particular usecontemplated. It is intended that the scope of the invention not belimited by the specification, but be defined claims set forth below.

1. A gas barrier film comprising a gas barrier laminate on a substratefilm, wherein: the gas barrier laminate comprises at least onethree-layer unit; the at least one three-layer unit consists of (a) afirst silicon nitride layer, (b) a silicon carbide compound layerdirectly on the first silicon nitride layer, and (c) a second siliconnitride layer directly on the silicon carbide compound layer; thesilicon carbide compound layer has a ratio between silicon atom andcarbon atom of 1:1 to 10:1; at least one of the first or second siliconnitride layers comprises 98 mass % or more of silicon and nitrogencombined; the silicon carbide layer comprises 98 mass % or more ofsilicon, oxygen and carbon combined; and the silicon carbide layercontains 10% or more of oxygen.
 2. The gas barrier film according toclaim 1, having a steam permeability at 40° C. and 90% relative humidityof 0.01 g/m²·day or less.
 3. The gas barrier film according to claim 1,wherein the substrate film is formed of a polymeric material having aglass transition temperature of 120° C. or higher.
 4. The gas barrierfilm according to claim 1, wherein at least one of the first or secondsilicon nitride layers in the gas barrier film is formed by inductivelycoupled plasma CVD.
 5. The gas barrier film according to claim 1,wherein the silicon carbide compound contains oxygen atom and theconstituent ratio of carbon atom and oxygen atom is form 1:1 to 1:5. 6.The gas barrier film according to claim 1, wherein the substrate filmcomprises a polymer having a structure represented by the followingformula (1) or a polymer having a structure represented by the followingformula (2):

wherein a ring α represents a mononuclear or polynuclear ring and tworings may be identical or different with each other and are bonded byspiro bonding,

wherein a ring βand a ring γeach represents a mononuclear or polynuclearring, two rings γmay be identical or different with each other andconnected to one quaternary carbon on the ring β.
 7. The gas barrierfilm according to claim 1, wherein a transparent conductive layer isdisposed on the gas barrier laminate.
 8. The gas barrier film accordingto claim 1, manufactured by a method of supplying the substrate film ina roll-to-roll system and forming the gas barrier laminate continuously.9. A substrate film for use in an image display device using the gasbarrier film according to claim
 1. 10. An organic electroluminescencedevice using the substrate film for use in an image display deviceaccording to claim
 9. 11. An organic electroluminescence devicemanufactured by forming the organic electroluminescence device accordingto claim 10, then disposing at least one three-layer unit in which asilicon nitride layer, a silicon carbide compound layer, and a siliconnitride layer are disposed in this order adjacent with each other invacuum without exposing to atmospheric air and then sealing the same.12. The gas barrier film according to claim 1, wherein the siliconcarbide layer has a Si/C ratio of 2 to
 5. 13. The gas barrier filmaccording to claim 1, wherein the silicon carbide layer is representedby formula Si_(y)O_(z)C_(w), wherein: r =(2z+4w)/y, 3.15<r≦4.0, and y/wis 2 to
 5. 14. The gas barrier film according to claim 1, wherein thesubstrate film has a glass transition temperature of 200° C. or higher.